Aqueous Solutions of Electrolytes

Содержание

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LESSON OBJECTIVES: Concept of electrolytes Define electrolyte, electrolytic solution, ion, cation,

LESSON OBJECTIVES:
Concept of electrolytes
Define electrolyte, electrolytic solution, ion, cation, anion
Arrhenius theory

of electrolytic dissociation
Acid and base
Ostwald’s dilution law
Ionic reactions in electrolyte solutions
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Electrolytes Substances which on dissolution, even at moderate dilution, ionize almost

Electrolytes

Substances which on dissolution, even at moderate dilution, ionize almost

completely

Substances which on dissolution in water, dissociate to a little extent

Strong electrolytes

Example:- HCl,HNO3,NaOH,NaCl,CaCl2 etc

Weak electrolytes

Example:-CH3COOH, NH4OH, AgCl etc

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In the world of chemistry, an electrolyte is a substance having

In the world of chemistry, an electrolyte is a substance having

the free ions so that the substance is electrical conductor. We can say that any substance, which furnishes ions in the solution, is called the electrolyte.
Due to the presence of free ions some of the solutions can pass electricity through them. As we can say that the pure distilled water is not an electrolyte but if we add some table salt, it becomes an electrolyte and the electric current pass through it.
The electrolyte is an ionic solution but the electrolytes can also be in molten and in the solid state.
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Pure water does not conduct an electric current Zumdahl, Zumdahl, DeCoste,

Pure water does not conduct an electric current

Zumdahl, Zumdahl, DeCoste, World

of Chemistry 2002, page 215

Ionic Solutions conduct a current

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Unlike charges (+ and –) attract one another. Like charges (+

Unlike charges (+ and –) attract one another.
Like charges

(+ and +, or – and –) repel one another.

Electrostatic Forces

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Electric current is a movement or flow of electrically charged particles

Electric current is a movement or flow of electrically charged particles

(electrons and ions), typically measured in:

Charged particles capable of conducting electrical current are called electrical conductors:
Metals are conductors of the first type with an electronic conductivity
Electrolytes are conductors of the second type with an ionic conductivity

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Ions are atoms (or groups of atoms) that carry electrical charge.

Ions are atoms (or groups of atoms) that carry electrical charge.


Positively (+) charged ions are called cations, whereas negatively (–) charged ions are called anions.

cations

anions

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Electrolytes are substances that dissociate into ions when dissolved in water

Electrolytes are substances that dissociate into ions when dissolved in water

and conduct electricity

Non-electrolytes are substances that do not form ions and do not conduct electricity when placed in water

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Electrical Conductivity of Ionic Solutions

Electrical Conductivity of Ionic Solutions

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The more the electrolyte dissociates, the more ions it produces.

The more the electrolyte dissociates, the more ions it produces.

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TYPES OF ELECTROLYTES A weak electrolyte dissociates partially. Weak electrolyte solutions

TYPES OF ELECTROLYTES
A weak electrolyte dissociates partially.
Weak electrolyte solutions are poor

conductors.
Different weak electrolytes dissociate to different extents.
Weak electrolytes include:
Weak acids and weak bases (NH4OH)
A few insoluble ionic compounds
A water H2O

A strong electrolyte dissociates completely.
A strong electrolyte is present in solution almost exclusively as ions.
Strong electrolyte solutions are good conductors.
Strong electrolytes include:
Strong acids (HCl, HBr, HI, HNO3, H2SO4, HClO4)
Strong bases (IA and IIA metals hydroxides)
Most water-soluble ionic compounds (salts)

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The Water Molecule is Polar dipol

The Water Molecule is Polar

dipol

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Water is “bent” or V-shaped. The O – H bonds are

Water is “bent” or V-shaped.
The O – H bonds are covalent.
Water

is a polar molecule.
Hydration occurs when salts dissolve in water.
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How Water Dissolves an Ionic Substance H2O hydrated cation hydrated anion

How Water Dissolves an Ionic Substance

H2O

hydrated cation

hydrated anion

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Этапы электролитической диссоциации полярных молекул (а) и ионных кристаллов (б): I

Этапы электролитической диссоциации полярных молекул (а) и ионных кристаллов (б): I

– сольватация; II – ионизация; III – диссоциация.

Теория электролитической диссоциации

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In order to explain the properties of electrolytic solutions, Arrhenius put

In order to explain the properties of electrolytic solutions, Arrhenius put

forth, in 1884, a comprehensive theory which is known as theory of electrolytic dissociation or ionic theory.

ARRHENIUS THEORY OF ELECTROLYTIC DISSOCIATION

Svante Arrhenius, 
Swedish chemist and
 Nobel laureate, 
1859-1927.

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THE MAIN POINTS OF THE THEORY ARE: An electrolyte, when dissolved

THE MAIN POINTS OF THE THEORY ARE:
An electrolyte, when dissolved in

water, breaks up into two types of charged particles. These charged particles are called ions.
When an electric current is passed through the electrolytic solution, the positive ions (cations) move towards cathode and the negative ions (anions) move towards anode and get discharged, i.e., electrolysis occurs.
The process of splitting of the electrolytes molecules into ions under the influence of polar molecules of solvent is called ionization (dissociation):

cation

anion

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The properties of electrolytes in solution are the properties of ions

The properties of electrolytes in solution are the properties of ions

present in solution. For example, acidic solution always contains H+ ions while basic solution contains OH- ions and characteristic properties of solutions are those of H- ions and OH- ions respectively.
The ions act like molecules towards depressing the freezing point, elevating the boiling point, lowering the vapour pressure and establishing the osmotic pressure.
The conductively of the electrolytic solution depends on the nature and number of ions as the current is carried through solution by the movement of ions.
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An acid is a substance that increase H+ when dissolved in

An acid is a substance that increase H+ when dissolved in

water:

Some acids have more than one ionizable hydrogen atom. They ionize in “steps”:
H2SO4 → H+ + HSO4–
HSO4– → H+ + SO42–

hydrogen sulfate ion

sulfate ion

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Strong acids are strong electrolytes; completely ionized in water: In water:

Strong acids are strong electrolytes; completely ionized in water:
In water: HCl(g)

→ H+(aq) + Cl–(aq)

Weak acids are weak electrolytes. Some of the dissolved molecules ionize; the rest remain as molecules.
In water: CH3COOH(l)  H+(aq) + CH3COO–(aq)

No HCl in solution, only H+ and Cl– ions.

Just a little H+ forms.

Reactions of Acid: Strong and Weak Acids

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A base is a substance that increase OH- when dissolved in

A base is a substance that increase OH- when dissolved in

water:

An ampholyte is a substance dissolving in water to OH- and H+ ions:

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Strong bases: Most are ionic hydroxides (Group IA and IIA, though

Strong bases: Most are ionic hydroxides (Group IA and IIA, though

some IIA hydroxides aren’t very soluble).
Weak bases: Like weak acids, they ionize partially. Ionization process is different.
Weak bases form OH– by accepting H+ from water …
NH3 + H2O  NH4+ + OH–
CH3NH2 + H2O  CH3NH3+ + OH–
methylamine methylammonium ion

Strong and Weak Bases

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Common Strong Acids and Strong Bases A pragmatic method of determining

Common Strong Acids and Strong Bases

A pragmatic method of determining whether an

acid is weak … just learn the strong acids!
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Strength and properties of the electrolyte are described by the following

Strength and properties of the electrolyte are described by the following

values:
the degree (α) of ionization
and the dissociation constant (Kdiss) of the electrolyte.
Degree of ionization 'α' may be defined as a fraction of total number of molecules of an electrolyte which dissociate into ions:
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Values of the degree of dissociation (ex)depends upon the following factors

Values of the degree of dissociation (ex)depends upon the following factors
nature

of solute
2. nature of solvent
3. concentration
4. temperature
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When temperature is increased, degree of ionization increase too When concentration

When temperature is increased, degree of ionization increase too

When concentration

is increased, degree of ionization decrease
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Dissociation is reversible process. Ions present in solution constantly re-unite to

Dissociation is reversible process. Ions present in solution constantly re-unite to

form neutral molecules and, thus, there is a state of dynamic equilibrium between the ionized and non-ionized molecules, i.e.,  AxBy  → x A+ + y B-
Applying the law of mass action to above equilibrium, we have constant K is known as ionization constant :
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For strong electrolytes α>0,3 (30%) and they having high value of Kdiss For weak electrolytes α

For strong electrolytes α>0,3 (30%) and they having high value of Kdiss


For weak electrolytes α<0,3 (0 – 30%) and those having low constant value of Kdiss
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OSTWALD'S DILUTION LAW For strong electrolytes: where K is dissociation constant

OSTWALD'S DILUTION LAW

For strong electrolytes:
where K is dissociation constant and C

is molar concentration of the solution.

This law is based on the fact that only a portion of the electrolyte is dissociated into ions at ordinary dilution and completely at infinite dilution. Strong electrolytes are almost completely ionized at all dilutions and λ/λ∞ does not give an accurate value of 'α'.
When the concentration of ions is very high, the presence of charges on the ions appreciably affects the equilibrium. Hence, law of mass action cannot be strictly applied in the case of strong electrolytes.

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OSTWALD'S DILUTION LAW For weak electrolytes (Kdiss=const and (1 – α)

OSTWALD'S DILUTION LAW

For weak electrolytes (Kdiss=const and (1 – α) ≈

1):

Thus, degree of dissociation of a weak electrolyte is proportional to the square root of dilution.
“For a weak electrolyte, the degree of ionisation is inversely proportional to the square root of molar concentration or directly proportional to the square root of volume containing one mole of the solute.” This is called Ostwald’s dilution law.

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A chemical equation which shows dissociation of electrolyte and written as

A chemical equation which shows dissociation of electrolyte and written as

dissociated ions of electrolyte is known as ionic equation.
Double Replacement (Metathesis) Reactions involve swapping ions in solution:
AX + BY → AY + BX

IONIC REACTIONS

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Metathesis reactions will lead to a change in solution if one

Metathesis reactions will lead to a change in solution if one

of three things occurs:
An insoluble solid is formed (When a chemical reaction forms such a solute, the insoluble solute comes out of solution and is called a precipitate),
Weak acids are formed (H2SO3, CH3COOH),
An insoluble gas is formed (H2S, CO2, SO2, NH3),
Neutralization reaction
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Irreversible reaction Precipitate(↓) BaCl2 + Na2SO4 = BaSO4 ↓ + 2NaCl

Irreversible reaction

Precipitate(↓)

BaCl2 + Na2SO4 = BaSO4 ↓ + 2NaCl

Gas reaction


Na2S+ 2HCl = H2S↑ + 2NaCl

Weak electrolytes are
formed

2CH3COOK + H2SO4 =
= 2CH3COOH + K2SO4

Complex compounds
are formed

Hg(NO3)2 + 4KJ = K2[HgJ4] +2KNO3

IONIC REACTION

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Neutralization is the (usually complete) reaction of an acid with a

Neutralization is the (usually complete) reaction of an acid with a

base. The products of this neutralization are water and a salt.

Acid–Base Reactions: Neutralization

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In the reaction above, the HCl, NaOH, and NaCl all are

In the reaction above, the HCl, NaOH, and NaCl all are

strong electrolytes and dissociate completely.
The actual reaction occurs between ions.

Acid–Base Reactions: Net Ionic Equations

HCl + NaOH ? H2O + NaCl

H+ + Cl– + Na+ + OH– ? H2O + Na+ + Cl–

H+ + OH– ? H2O

A net ionic equation shows the species actually involved in the reaction.

Na+ and Cl– are spectator ions.

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There are limits to the amount of a solute that will

There are limits to the amount of a solute that will

dissolve in a given amount of water.
If the maximum concentration of solute is less than about 0.01 M, we refer to the solute as insoluble in water.
When a chemical reaction forms such a solute, the insoluble solute comes out of solution and is called a precipitate.

Reactions that Form Precipitates

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Silver Iodide Precipitation A solution containing silver ions and nitrate ions,

Silver Iodide Precipitation

A solution containing silver ions and nitrate ions, when

added to …

… a solution containing potassium ions and iodide ions, forms …

What is the net ionic equation for the reaction that has occurred here? (Hint: what species actually reacted?)

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With these guidelines we can predict precipitation reactions. When solutions of

With these guidelines we can predict precipitation reactions.
When solutions of sodium

carbonate and iron (III) nitrate are mixed, a precipitate will form.
When solutions of lead acetate and calcium chloride are mixed, a precipitate will form.